CN103041764A - Adsorbent for fuel oil desulfurization, preparation method and application thereof - Google Patents
Adsorbent for fuel oil desulfurization, preparation method and application thereof Download PDFInfo
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- CN103041764A CN103041764A CN2012105665661A CN201210566566A CN103041764A CN 103041764 A CN103041764 A CN 103041764A CN 2012105665661 A CN2012105665661 A CN 2012105665661A CN 201210566566 A CN201210566566 A CN 201210566566A CN 103041764 A CN103041764 A CN 103041764A
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- fuel oil
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- desulfurization
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- adsorption
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 107
- 239000000295 fuel oil Substances 0.000 title claims abstract description 92
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 53
- 230000023556 desulfurization Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 34
- -1 silver halide Chemical class 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 71
- 239000011593 sulfur Substances 0.000 claims description 51
- 229910052717 sulfur Inorganic materials 0.000 claims description 51
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000001179 sorption measurement Methods 0.000 claims description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 24
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 20
- 239000011780 sodium chloride Substances 0.000 claims description 16
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 15
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 235000009518 sodium iodide Nutrition 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical group [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 42
- 238000004817 gas chromatography Methods 0.000 description 21
- 239000012263 liquid product Substances 0.000 description 21
- 229930192474 thiophene Natural products 0.000 description 21
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 20
- 239000005864 Sulphur Substances 0.000 description 20
- 238000010790 dilution Methods 0.000 description 20
- 239000012895 dilution Substances 0.000 description 20
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 20
- 239000002594 sorbent Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses an adsorbent for fuel oil desulfurization. The adsorbent does not need any carrier, and only uses silver halide nanoparticles to adsorb and remove sulfides in fuel oil under mild conditions. The adsorbent for desulfurizing the fuel oil is silver halide nanoparticles.
Description
Technical field
The present invention relates to a kind of adsorbent, preparation method and application thereof, more specifically to a kind of adsorbent for the desulfurization of fuel oil, preparation method and application thereof, belong to desulfurization of fuel oil field.
Background technology
The oxysulfide that the sulfur-containing compound burning produces in the fuel oil (gasoline, diesel oil, kerosene etc.) enters atmosphere and can produce acid rain, and ground trees and building etc. are produced corrosion.Meanwhile oxysulfide also can corrode engine, and the performance of infringement lambda sensor and onboard diagnostic system makes the catalyst poisoning in the vehicle exhaust converter and affects the performance performance of catalytic converter.In addition, the New-type fuel technology such as fuel cell has also proposed very high request to the sulfur content in the fuel oil.Along with people in the global range are more and more higher to the cry of environmental protection, people have proposed more and more higher requirement to the quality of fuel oil simultaneously, and various relevant laws and regulations are also put into effect in succession.Therefore, must remove to produce to the sulfur-containing compound in the fuel oil needs that the cleaning of low sulfur content, super clean fuel oil satisfy productive life.
Present desulfur technology is take the hydrodesulfurization technology as main, although for most sulfide in the fuel oil preferably removal effect is arranged, but the removal effect for thiophene-type sulfide is poor, and the operating condition of HTHP not only cost is higher, and can cause the octane number of fuel oil to reduce.The adsorption desulfurize technology has mild condition, and technique is simple, and adsorbent is the advantage such as regeneration easily, becomes the focus of Recent study.Adsorbent is the core technology of adsorption desulfurize process, and the exploitation of new and effective sorbing material gets more and more people's extensive concerning.Document (Ind.Eng.Chem.Res., 2003,4:123) disclose a kind of AgY adsorbent and removed thiophene in the analog fuel oil, show good absorption property.Document (Chem.Eng.Sci., 2009,64:5240) disclose a kind of with AgNO
3Load on mesopore molecular sieve MCM-41 and the SBA-15, remove sulfide in the JP-5 fuel oil light component as adsorbent, show good adsorption desulfurize performance.But above-mentioned adsorbent must be with active component A gNO
3Load on and carry out desulfurization, AgNO on the carrier
3Particle diameter own very much not possesses good adsorption activity.And adsorption desulfurize performance and the deployment conditions of active specy on carrier have much relations, if disperse bad, active specy can not fully contact with fuel oil, will not reach desirable desulfurized effect.
Most of research work all concentrates in the preparation and application of load type adsorbing agent in the adsorption desulfurize technology up to now, not yet sees the report that openly need not carrier and directly remove thiophene-type sulfide with nano particle by absorption method.
Summary of the invention
The objective of the invention is to be to provide a kind of adsorbent for the desulfurization of fuel oil.This adsorbent need not any carrier, only under the condition of gentleness the sulfide in the fuel oil is carried out adsorbing and removing with the silver halide nano particle.
Another object of the present invention provides the preparation method of above-mentioned adsorbent.
A further object of the invention provides utilizes above-mentioned adsorbent to carry out the method for adsorption desulfurize.
The objective of the invention is to be achieved through the following technical solutions:
Adsorbent for the desulfurization of fuel oil of the present invention, its described adsorbent is the silver halide nano particle.
Adsorbent for the desulfurization of fuel oil of the present invention, its further technical scheme be that the particle diameter of described silver halide nano particle is 50～800nm, described silver halide is preferably silver chlorate, silver bromide or silver iodide.
The preparation method of the adsorbent that is used for the desulfurization of fuel oil that the present invention is above-mentioned, it may further comprise the steps:
Silver nitrate and sodium halide are dropwise joined in the aqueous surfactant solution, behind the lucifuge stirring reaction, pass through again centrifugal, alcohol wash and lucifuge drying after, namely obtain this adsorbent.
The preparation method of the adsorbent for the desulfurization of fuel oil of the present invention, the mol ratio that its further technical scheme is described silver nitrate and sodium halide is 0.5～2.0, described sodium halide is sodium chloride, sodium bromide or sodium iodide.
The preparation method of the adsorbent for the desulfurization of fuel oil of the present invention, its further technical scheme can also be that described surfactant is tetradecyl trimethyl ammonium chloride (TTAC), hexadecyltrimethylammonium chloride (CTAC) or OTAC (OTAC), and the concentration of aqueous surfactant solution is 9.2 * 10
-4～2.76 * 10
-3Mol/L, volume are 97mL.
The preparation method of the adsorbent for the desulfurization of fuel oil of the present invention, the reaction temperature that its further technical scheme is described lucifuge stirring reaction is 25～80 ℃, the reaction time is 0.5～5.0h.
The invention also discloses this and be used for the adsorbent of the desulfurization of fuel oil in the application of fuel oil adsorption-desulfurization.
The application of adsorbent of the present invention in fuel oil adsorption-desulfurization, it may further comprise the steps: with the fuel oil joint of described adsorbent and sulfur-bearing, utilize adsorption method of separation to realize the desulfurization of fuel oil.Liquid product is measured its sulfur content with Varian 3800 gas-chromatographies.
The application of adsorbent of the present invention in fuel oil adsorption-desulfurization, the fuel oil joint condition that its further technical scheme is described adsorbent and sulfur-bearing is as follows: temperature is room temperature～50 ℃, and pressure is normal pressure～0.5MPa.
The application of adsorbent of the present invention in fuel oil adsorption-desulfurization, the fuel oil that its further technical scheme can also be described sulfur-bearing is the fuel oil that contains thiophene-type sulfide.
Compared with prior art the present invention has following beneficial effect:
The present invention proposes a kind of simple method, the coprecipitation auxiliary by surfactant prepares the AgX nano particle, this method only needs to add a kind of surfactant in building-up process, need not cosurfactant and oil phase, have easy to prepare, reaction condition is gentle, do not need the characteristics such as HTHP.The nano particle diameter of preparing is controlled and be evenly distributed, and can obtain the particle of different-grain diameter size and pattern by the conditioned reaction temperature, does not reunite between the nano particle and has good dispersiveness.The present invention is directly used in the adsorption desulfurize of fuel oil with the nanometer Ag X particle that is synthesized, and is different from traditional load type adsorbing agent.This adsorbent is large to the adsorption capacity of thiophene-type sulfide, and desulfuration efficiency is high.Adsorption conditions can carry out under normal temperature and pressure conditions, and running cost is low.Adsorbent of the present invention does not need activation simultaneously, can be directly used in adsorption desulfurize after synthesizing.
The specific embodiment
The following examples will be further described the present invention, but content of the present invention is not limited to this fully.
Embodiment 1
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.25mol/L are dropwise joined 97mL9.2 * 10
-4In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 0.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, stirring reaction 7h under the room temperature normal pressure, get liquid product and measure its sulfur content with Varian 3800 gas-chromatographies, desulfurization amount is 93 μ mol sulphur/g adsorbents (adsorbances the when desulfurization amount of the statement among the application is the adsorbent saturated adsorption, lower same).
Embodiment 2
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.25mol/L are dropwise joined 97mL9.2 * 10
-4In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 2h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 102 μ mol sulphur/g adsorbents.
Embodiment 3
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.25mol/L are dropwise joined 97mL9.2 * 10
-4In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 131 μ mol sulphur/g adsorbents.
Embodiment 4
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.25mol/L are dropwise joined 97mL9.2 * 10
-4In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 125 μ mol sulphur/g adsorbents.
Embodiment 5
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL9.2 * 10
-4In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 156 μ mol sulphur/g adsorbents.
Embodiment 6
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 1mol/L are dropwise joined 97mL9.2 * 10
-4In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 117 μ mol sulphur/g adsorbents.
Embodiment 7
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 184 μ mol sulphur/g adsorbents.
Embodiment 8
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL2.76 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 25 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 157 μ mol sulphur/g adsorbents.
Embodiment 9
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 40 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 491 μ mol sulphur/g adsorbents.
Embodiment 10
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 60 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL simulation vapour fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 372 μ mol sulphur/g adsorbents.
Embodiment 11
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 80 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 256 μ mol sulphur/g adsorbents.
Embodiment 12
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the TTAC aqueous solution of mol/L, add ethanol washing 3 times after 40 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 419 μ mol sulphur/g adsorbents.
Embodiment 13
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the OTAC aqueous solution of mol/L, add ethanol washing 3 times after 40 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 427 μ mol sulphur/g adsorbents.
Embodiment 14
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium chloride of 1mL 0.5mol/L is miscible, after stirring 3.5h, be centrifugal, 40 ℃ of lower lucifuges add ethanol washing 3 times, and the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 86 μ mol sulphur/g adsorbents.
Embodiment 15
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium bromide of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 40 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 467 μ mol sulphur/g adsorbents.
Embodiment 16
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium bromide of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 60 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 356 μ mol sulphur/g adsorbents.
Embodiment 17
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium bromide of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 80 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 232 μ mol sulphur/g adsorbents.
Embodiment 18
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium iodide of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 40 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with Varian 3800 gas-chromatographies, and desulfurization amount is 453 μ mol sulphur/g adsorbents.
Embodiment 19
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium iodide of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 60 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with the Varian3800 gas-chromatography, and desulfurization amount is 347 μ mol sulphur/g adsorbents.
Embodiment 20
The preparation of adsorbent: silver nitrate and the 1mL 0.5mol/L sodium iodide of 1mL 0.5mol/L are dropwise joined 97mL1.84 * 10
-3In the CTAC aqueous solution of mol/L, add ethanol washing 3 times after 80 ℃ of lower lucifuges stir 3.5h, be centrifugal, the room temperature lucifuge is dry, namely obtains sample of sorbent.
Adsorption experiment: the 5mL thiophene is dissolved in the 45mL isooctane, and dilution is made into the analog fuel oil that sulfur content is 550ppm.The 0.04g adsorbent is joined in the 10mL analog fuel oil, and stirring reaction 7h under the room temperature normal pressure gets liquid product and measures its sulfur content with the Varian3800 gas-chromatography, and desulfurization amount is 239 μ mol sulphur/g adsorbents.
Claims (10)
1. an adsorbent that is used for the desulfurization of fuel oil is characterized in that described adsorbent is the silver halide nano particle.
2. the adsorbent for the desulfurization of fuel oil according to claim 1, the particle diameter that it is characterized in that described silver halide nano particle is 50～800nm, described silver halide is silver chlorate, silver bromide or silver iodide.
3. the preparation method of the adsorbent for the desulfurization of fuel oil as claimed in claim 1 or 2 is characterized in that may further comprise the steps:
Silver nitrate and sodium halide are dropwise joined in the aqueous surfactant solution, behind the lucifuge stirring reaction, pass through again centrifugal, alcohol wash and lucifuge drying after, namely obtain this adsorbent.
4. the preparation method of the adsorbent for the desulfurization of fuel oil according to claim 3, the mol ratio that it is characterized in that described silver nitrate and sodium halide is 0.5～2.0, described sodium halide is sodium chloride, sodium bromide or sodium iodide.
5. the preparation method of the adsorbent for the desulfurization of fuel oil according to claim 3, it is characterized in that described surfactant is tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride or OTAC, the concentration of aqueous surfactant solution is 9.2 * 10
-4～2.76 * 10
-3Mol/L, volume are 97mL.
6. the preparation method of the adsorbent for the desulfurization of fuel oil according to claim 3, the reaction temperature that it is characterized in that described lucifuge stirring reaction is 25～80 ℃, the reaction time is 0.5～5.0h.
7. the adsorbent for the desulfurization of fuel oil as claimed in claim 1 or 2 is in the application of fuel oil adsorption-desulfurization.
8. the application of adsorbent according to claim 7 in fuel oil adsorption-desulfurization is characterized in that may further comprise the steps: with the fuel oil joint of described adsorbent and sulfur-bearing, utilize adsorption method of separation to realize the desulfurization of fuel oil.
9. the application of adsorbent according to claim 8 in fuel oil adsorption-desulfurization is characterized in that the fuel oil joint condition of described adsorbent and sulfur-bearing is as follows: temperature is room temperature～50 ℃, and pressure is normal pressure～0.5MPa.
10. according to claim 8 or 9 application of described adsorbent in fuel oil adsorption-desulfurization, the fuel oil that it is characterized in that described sulfur-bearing is the fuel oil that contains thiophene-type sulfide.
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| CN110354809A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | One kind is with SiO2- APTES-Ag composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
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